Treatment of hydrocarbon oils



July 14, 1942. K. M. THOMPSON TREATMENT OF HYDBOCARBON OILSl Filed March ll, 1940 lcarrying out my process.

j QUNITED; STATES TREATMENT '0F iiYnRooAaBoN oiLs "Kenneth M. Thompson, Aidan, Paf., assgnor to The Atlantic Refining Company, Philadelphia,"` l Pai, acorporation of Pennsylvania 1 aopiioatiohriarh 11,

1940,se r1iaiso. 323.27'5

The present inventionfrelates to the treatment of hydrocarbonsffor the` purpose of producing therefrom an'4 improved type of motor fuel. In' its more specific" aspects, the present invention re'- latesftothe treatment of hydrocarbons of the gasoline type to convert` the same into gasoline having improved anti-knock qualities.

In accordance with the present invention, gasav oline distillates having a'. boiling range of the` order of 100 F. to400 F., or heavy naphthas sores of thoorder or sono iba/so; in. Theheated mixtureisV passed through the catalyst bed at a` temperatureiof the order of 1000,F.and .re-

commonlyfdesignated asl reformersto'cks are subjected toa` reforming treatment for the irnprovement of the anti-knock qualities thereof.' Such treatment comprises essentially a thermal reforming operationwherein the hydrocarbon distillate is brought into contact, at elevated temperatures, with a reforming catalyst in the presence of added quantities of earboxi disulfide for a period of time suiiicient to increase the anti-` knock value of the distillate to a substantial extent.i The thermal treatment may be eiectedv at temperatures of from about 750 F; to` about 1200o F., and preferably atfrom about 900 F. to about 1000 F. Reforming catalysts ofthe nature of adsorbent earths, such as fullersearth, are preferred, although other agents such as acid activated clays, bentonite, bauxite, silica geLYsynthetic silicates, and the like may be' utilized. The quantity of carbon disulde employed may vary from about 0.1 `to about 10% by weight of the hydrocarbon distillate, the preferred amount being from about`0;2% `to aboutl 3%l byweight. The ,improved distillate froml the reforinf ing operation-may be rerun "and/or otherwise treatedoto obtaina motor fuel of desiredboiling range havinga substantially reduced" 'content of the like.

Myl invention may be 'further understood with reference vto Vthe accompanying drawing, `which represents diagrammatically a system suitable for ''hahydrocarbon distillate pipes` I `and v2;resl'iectively. The mixture of dis tillate and CS2 is forced through the heating coil l `to be treated,` and* I the desired quantity ofCSz may be simultaneously .suppliedbtopurnp 3 by` means of valve-controlled lIl rmeans of valve-controlled pipe i1.

formingfof the distillate therein takes place. As arsult of the reforming reaction, molecular rearrangement ofv the hydrocarbons comprising the distillate occurs, with theevolution of gasesinfV cluding H255.1 The mixture resulting froml the reforming "reactionj includingv reformed distillate,

traces-of unreact-edCSz; and byproducts of the reaction is Withdrawn from the bottom of tower Tand passed through valve-controlled pipe 9 intol fractionatinglcollimn II), wherein the distillate boilingvpolymers resulting from, the vcatalytic treatment. Such polymers may be' removedfrom the bottom'f column Ill by means of valve-controlled pipe H,jwhile the reformed hydrocarbon distillate of desired boiling range and gaseous reactionproducts maybe Withdrawn from the "top o'fthe column IU in a vaporous,state.V The vaporsand'gases may be conducted by valve-V controlled pipe I2.and.pipe I3 tocondenser I4 wherein :thehydrocarbon Avapors are condensed, and the liquid condensatejand unccndensed gases are'lpassed by pipe I5 into separator I6." f Inysep.-

varator I6? the condensate, i. e.,\.the reformed" hyv drocarbon distillate, is separated from the uncondens'ed gases and is withdrawn therefrom by Such `reformed distillate may be treated for the removal of-acid gases Asuch as HzS by neutralization'with "caustic soda solution and water washing, the resulting distillate vbeing a motor fuelof improved anti-knockvaluen The uncondensed gases accumulating infthe 4lupper'portionfof separator lli may be vented-by means` of val-ve.-controlled.` pipe I8", or may be 'recirculated to the thermal reforming system'by `onefor both of the `followingprocedures.` 0r,l a

portion of the g'asesvrnay be vented and the remaindcr mayberecirculated. Uncondensed gases ",rnaybe W-ithdrawn fromfthe'topof separator Il` i through Ipipe/IS and passed by valve-controlled pipe'nto thev inlet side of pump 3 for recirculat. tion through `the heating coill. Or; the unconl disposed in furnace l.'a, wherein 4the temperael ture of. the mixture is raised to about 1000" and the heated mixture is passedjthroughpipe E intoa catalytic treatment tower I `containing a bed of granularcatalyst 8 'such as `4;--8- mesh fullers earth. The' operating pressure within the heating coil l and the catalytic tower 1 may v'ary from slightly superatinospheric up to presdensed gases may be passed through pipe llland valve-controlled pipe 2l to pump 22, and forced thereby through valvofcontroui .proeza into' pipe 1 8 carrying heated hydrocarbon vdistillate from coil `4' to catalytic towerv 1. IfdesiredyI may introduce untreated `distillate fromv valve-controlled taneous introduction of `CS2 through vvalve-controlled pipe .2. Inthis case I may supply C'Sz f l 2,289,530 f I v earth, per se.

l1 may be neutralized and washed'to` remove acid gases and sulfur compounds, and may thereafter be rerun in suitable distillationn equipment to rei".

move high boiling polymers andpr'odu'ce'a motor* fuel of proper boiling range and improved antiknock quality. f

My invention may be further illustrated by the yfollowing examples, which include runs made f" with-'fullers earth and CSi'fullers earth Withwith fulls earth `and- CS2, fullers earth with; hydrocarbon distillate employed-had a boiling. ran eof"'l2 0 F.to335 -an;A. P. I. gravity .'.of 5 918"flairt 'anti-kritiek` or octane value .of. 5 7.' vand a sillfrcontent of"0.05'1\%'.- The ytreatment comprisedvaporizing the untreated distillate, passing thel vapors 'a't substantially atmospheric pressurev thrlcugh a bed of -4-8 mesh fullers earthinaintained at a temperatureofithe order-of .99 0 F. to 1000" F., 'condensing raw` condensatewith :caustic soda solution and with Water, and thereafter rerunning the raw condensate, Without'A fractionation, to produce a finished gasoline having a`320 F. distillationend prises intimately contacting said distillate, in the presence of added carbon bisulde and in the absence of hydrogen introduced ous source, with an incombustible solid adsorbent reforming catalyst at a temperature within the range of from about 750 F. to about 1200" F.

2. The method of reforming petroleum distillate comprising hydrocarbons boiling substantially within the gasoline boiling range to improve the anti-knock quality thereof, which comprises intimately contacting said distillate, in the presence ofadded'carbon bisulde'and in the absence of hydrogen introduced from an extraneous source, with an incombustible solid adsorbent reforming catalyst at a temperature within l the range of from' about '750 F. to about 1200 F., andv separating from the treated distillate a gasoline fraction of improved anti-knock quality. v "3.-The'method ofreforming petroleum distillate comprising hydrocarbons boiling substantially within the gasoline boiling range to improve the anti-knock quality thereof, which comprises intimately contacting said distillate, in the presence of from about 0.1% to about 10% by weight of carbonbisulflde and in the absence of hydrogen introduced from 'an extraneous source,

with 'an incornbustible solid adsorbent reforming from about '150 catalyst "at a temperature within the range of to about 1200 F.l

fl. The methodof reforming petroleum late comprising hydrocarbons boiling substantially` within the' gasoline boiling range to im- `the vapors, washing the i prove the anti-knock quality thereof, which comprises intimately c'ontacting said-distillate, in the presence of from about 10.1% to about 10% by Weight of carbonbisulfide and in the absence of hydrogen introduced from `an extraneous source,

point. with an argillaceous reforming catalyst at a temi f l l Treatment Treated distillate "I Catalyst -v Wei V ght Contact Yield Yigld Octane Peggy?. me vtime (raw) egfpgt am *Sulfug F`. v Seconda Percent. Percent Percent 2164 1,000 2.9 98.0 97.0 .-57 1.92

0.0 995 3.0 96.0 95.0 58.5 0.013 0.1 1,000 3.2 92.0 91.7 ci 0.024: 0.2 996 33.1* `92A` 89.0 62.7 0.022 05,34 1,000 3.1 87.0 84.4 64. 3' 0.050

results', lit will befseen `that in accordance with my invention, able to effect While, hereinabov -boiling substantiallywithinfthe4 gaso- `frox'n' 4about 100 .il el, and'whicli may lbe produced` by j distillation,I cracking, hydrogenation; ypolymerization, or alkylationfof' petroleum hydrocarbons.

l. -j 1. :rue methodw of.,rerdrmingfpetrieum diste:4

Ilate [comprising hydrocarb g tiauywithifi the g ons boiling substanas olin'e' boiling 'range to improve thefantifknocl; quality thereof, which com- `perature within the range of from about'750 F.

toabout11200 F. v

5.- The method of reforming petroleum distillate .comprising hydrocarbons boiling substantially within the gasoline boiling rangeV'to improve .theanti-knock duality thereof, which com- 1 weight o f carbon prises intimately contacting said distillate, in the presence of from about 0.1% to about 10% by bisulde and in the absence of hydrogen introduced from anextraneous source, with fullers earth at a temperature within'the range of from about 7 I. 6. The methodof reforming petroleum distilllatelcomprising hy .tially within the gaso provethe anti-knock'quality thereof,

drocarbons boiling substanlineV boiling range to' imwhichcomprises. intimately contacting said distillate, in the -presenceof from about 0.2% to about 3.0% by weight of carbon bisuliide and in the absence of hydrogen introduce d from an extraneoussource, withv fullers earth at a temperature of from about 900"v F. to about 1000 F.

from an extrane- I distri-'7 7. Thel method of reforming petroleum distillate comprising hydrocarbons boiling substan-Q tially within the gasoline boiling range to improve the anti-knock quality thereof, which comprises intimately contacting said distillate, in the presence of from about 0.2% to about 3.0% by` Weightof carbon bisulde and inthe absenceof 5 improved anti-knock quality.

KENNETH M. THOMPSON. 

